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| Title: | Aluminium Complexes Containing Bidentate and Symmetrical Tridentate Pincer Type Pyrrolyl Ligands: Synthesis, Reactions and Ring Opening Polymerization |
| Authors: | Huang, Wen-Yen;Chuang, Sheng-Jie;Chunag, Nien-Tsu;Hsiao, Ching-Sheng;Datta, Amitabha;Chen, Shau-Jiun;Hu, Ching-Han;Huang, Jui-Hsien;Lee, Ting-Yu;Lin, Chia-Her |
| Contributors: | 化學系 |
| Date: | 2011
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| Issue Date: | 2012-12-10T01:39:58Z
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| Publisher: | Royal Society of Chemistry |
| Abstract: | A series of aluminium derivatives containing substituted bidentate and symmetrical tridentate pyrrolyl ligands, [C4H3NH(2-CH2NHtBu)] and [C4H2NH(2,5-CH2NHtBu)2], in toluene or diethyl ether were synthesized. Their reactivity and application for the ring opening polymerization of ε-caprolactone have been investigated. The reaction of AlMe3 with one equiv. of [C4H3NH(2-CH2NHtBu)] in toluene at room temperature affords [C4H3N(2-CH2NHtBu)]AlMe2 (1) in 70% yield by elimination of one equiv. of methane. Interestingly, while reacting AlMe3 with one equiv. of [C4H3NH(2-CH2NHtBu)] in toluene at 0 °C followed by refluxing at 100 °C, [{C4H3N(2-CH2NtBu)}AlMe]2 (2) has been isolated via fractional recrystalliztion in 30% yield. Similarly, reacting AlMe3 with two equiv. of C4H3NH(2-CH2NHtBu) generates [C4H3N(2-CH2NHtBu)]2AlMe (3) in a moderate yield. Furthermore, complex 1 can be transformed to an aluminium alkoxide derivative, [C4H3N(2-CH2NHtBu)][OC6H2(-2,6-tBu2-4-Me)]AlMe (4) by reacting 1 with one equiv. of HOC6H2(-2,6-tBu2-4-Me) in toluene via the elimination of one equiv. of methane. The reaction of AlR3 with one equiv. of [C4H2NH(2,5-CH2NHtBu)2] in toluene at room temperature affords [C4H2N(2,5-CH2NHtBu)2]AlR2 (5, R = Me; 6, R = Et) in moderate yield. Surprisingly, from the reaction of two equiv. of [C4H2NH(2,5-CH2NHtBu)2] with LiAlH4 in diethyl ether at 0 °C, a novel complex, [C4H2N(2-CH2NtBu)(5-CH2NHtBu)]2AlLi (7) has been isolated after repeating re-crystallization. Furthermore, reacting one equiv. of C4H2NH(2,5-CH2NHtBu)2 with AlH3·NMe3 in diethyl ether generates an aluminium dihydride complex, [C4H2N(2,5-CH2NHtBu)2]AlH2 (8), in high yield. Additionally, treating 8 with one equiv. of HOC6H2(-2,6-tBu2-4-Me) in methylene chloride produces [C4H2N(2,5-CH2NHtBu)2][OC6H2(-2,6-tBu2-4-Me)]AlH (9) with the elimination of one equiv. of H2. The aluminium alkoxide complex 4 shows moderate reactivity toward the ring opening polymerization of ε-caprolatone in toluene. |
| Relation: | Dalton Transactions, 40: 7423-7433 |
| Appears in Collections: | [化學系] 期刊論文
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